The present invention relates to pump sprays, pump foams and leave-on hair treatment compositions all of which are free from propellant gas and comprise anionic and cationic polymers. U.S. Pat. No. 4,240,450 discloses mixtures and processes for treating keratin materials with polymers. The mixtures comprise an anionic and a cationic polymer. In many of the known mixtures this results in problems, in that the polymers are precipitated as solids in the mixtures. This necessitates a special application method. The known mixtures are intended in particular for what are known as rinse-off products, i.e. compositions, such as shampoos, which are applied and then washed off again. As compositions which remain on the hair only lotions are mentioned in column 51. Compositions which are free from propellant gas and are sprayed onto the hair are not disclosed. A host of very widely differing compounds are mentioned as possible polymers.
DE 32 17 059 C2 describes pressurized compositions for applying to hair that are in the form of an aerosol foam, with aerosol foam denoting a foam obtained with the aid of a conditioned agent which is under pressure. These compositions necessarily include a propellant. The use of propellants, however, is to be avoided on environmental grounds.
It is an object of the present invention to provide hair treatment compositions which can be applied by spraying even without a propellant gas, which are readily distributed on the hair, and which even under conditions of high atmospheric humidity provide a high level of stability to the hairstyle and at the same time permit good dry combability and elasticity of the hair. The intention is at the same time to ensure that a stable foam can be produced and that the compositions as leave-on products, i.e. as compositions which remain on the hair and are not washed off again after use, impart high flexural strength and little stickiness to the hair.
We have found that this object is achieved in accordance with the invention by hair treatment compositions in the form of pump sprays and pump foams that are free from propellant gas and comprise at least one cationic and at least one anionic polymer.
The hair treatment compositions of the invention in the form of pump sprays and pump foams surprisingly allow access, even without the use of the unwanted propellants, to sprayable compositions which lead to stable and yet light and readily distributed foams that feature good wet and dry combability and hairsetting and which improve the flexural strength of the hair without the occurrence of stickiness.
The hair treatment compositions of the invention can also be in the form of leave-on hair treatment compositions which are free from propellant gas and from polysiloxane and which comprise, dissolved in a solvent, a copolymer with vinylpyrrolidone units and a copolymer with methacrylic acid and ethyl acrylate units.
As the polymers it is possible to employ a large number of compounds which are known per se, for example, from DE 32 17 059.
Preference is given to the use of cationic polymers having a molecular weight (Mn) of from 500-1,000,000 and comprising primary, secondary, tertiary and/or quaternary amine groups. As anionic polymers it is preferred to employ polymers having a molecular weight (Mn) of from 500 to 1,000,000 which comprise sulfo, carboxyl or phosphoric acid groups.
Use is made in particular of cationic polymers of the following groups, which are mentioned in DE 32 17 059:
1) copolymers of vinylpyrrolidone-dialkylaminoalkyl methacrylate or acrylate which are unmodified or quaternized,
2) derivatives of cellulose ethers comprising quaternary ammonium groups, and quaternary cellulose derivatives,
3) cationic polysaccharides and cationic guar gum derivatives,
4)
cationic polymers selected from the group of polymers comprising groups of the formula xe2x80x94Axe2x80x94Zxe2x80x94Axe2x80x94Zxe2x80x94 (I) in which A is a radical having two amino groups, preferably piperazinyl, and Z is B or Bxe2x80x2 which are identical or different and are a linear or branched alkylene which is unsubstituted or substituted by hydroxyls and which may also include oxygens, nitrogens, sulfurs and/or from one to three aromatic and/or heterocyclic rings;
polymers of the formula xe2x80x94Axe2x80x94Z1xe2x80x94Axe2x80x94Z1xe2x80x94 (II) in which A is as defined above and Z1 is B1 or Bxe2x80x21 and on at least one occasion is Bxe2x80x21, where B1 is a linear or branched alkylene or hydroxyalkylene, Bxe2x80x21 is a linear or branched alkylene which is unsubstituted or substituted by one or more hydroxyls and is interrupted by one or more nitrogens, the nitrogen being substituted by an alkyl chain which is uninterrupted or interrupted by an oxygen and which if desired includes one or more hydroxyls;
alkylation products with alkyl or benzyl halides, lower-alkyl-tosylate or -mesylate, and oxidation products of the polymers of the formulae (I) and (II),
5) polyamino-polyamides,
6) crosslinked polyamino-polyamides from the following group
a) crosslinked, alkylated or nonalkylated polyamino-polyamides obtained by crosslinking a polyamino-polyamide prepared by polycondensation of an acidic compound and a polyamine with a crosslinking agent from the group of the epihalohydrins, diepoxides, dianhydrides, unsaturated anhydrides and bis-unsaturated derivatives, the crosslinking agent being used in amounts of from 0.025 to 0.35 mol per amine group of the polyaminoamide;
b) crosslinked polyamino-polyamides obtained by crosslinking a polyamino-polyamide as defined above with a crosslinking agent selected from the following group:
I bis-halohydrins, bis-azetidinium, bis-haloacyldiaminee, alkyl bis-halides,
II oligomers obtained by reacting a compound of group or epihalohydrins, diepoxides and/or bis-unsaturated derivatives with a bifunctional compound that is reactive toward these compounds,
III quaternization products of a compound of group I and of the oligomers of group II which comprise tertiary amine groups some or all of which are alkylatable with an alkylating agent, crosslinking being effected with the aid of from 0.025 to 0.35 mol-% of crosslinking agent per amine group of the polyaminoamide,
c) polyamino-polyamide derivatives obtained by condensing a polyalkylene-polyamine with a polycarboxylic acid and then alkylating the product using bifunctional agents of the type of the adipic acid-dialkylaminohydroxyalkyl-dialkylenetriamine copolymers,
7) polymers obtainable by (i) free-radically initiated copolymerization of monomer mixtures comprising
(a) from 1 to 99.99% by weight, preferably from 2 to 70% by weight and, with particular preference, from 2 to 50% by weight of a cationic monomer or quaternizable monomer,
(b) from 0 to 98.99% by weight, preferably from 22 to 97.98% by weight and, with particular preference, from 45 to 97.95% by weight of a water-soluble monomer,
(c) from 0 to 50% by weight, preferably from 0 to 40% by weight, with particular preference, from 0 to 30% by weight of a further free-radically copolymerizable monomer, and
(d) from 0.01 to 10% by weight, preferably from 0.02 to 8% by weight, and, with particular preference, from 0.05 to 5% by weight of a bifunctional or higher polyfunctional, free-radically copolymerizable monomer,
and (ii) subsequent quaternization of the polymer if the monomer (a) employed was a non-quaternized monomer.
Suitable monomers (a) are the N-vinylimidazole derivatives of the formula (I) where R1 to R3 are hydrogen, C1-C4-alkyl or phenyl 
Also suitable are diallylamines of the formula (II) where R4 is C1-C24-alkyl. 
Also suitable are N,N-dialkylaminoalkyl acrylates and methacrylate, and N,N-dialkylaminoalkylacrylamides and methacrylamides, of the formula (III), 
where R5 and R6 independently are hydrogen or methyl, R7 is C1-C24-alkylene optionally substituted by alkyls and R8 and R9 are C1-C24-alkyl, Z being a nitrogen together with x=1 or an oxygen together with x=0.
The quaternization of the monomer or of a polymer with one of these quaternizing agents can take place in accordance with conventional methods.
Preferred quaternizing agents are methyl chloride, dimethyl sulfate or diethyl sulfate.
Preferred examples of monomers (a) are 3-methyl-1-vinylimidazolium chloride and methosulfate, dimethyldiallylammonium chloride and also N,N-dimethylaminoethyl methacrylate and N-[3-(dimethylamino)propyl]methacrylamide which have been quaternized by methyl chloride, dimethyl sulfate or diethyl sulfate.
Suitable water-soluble monomers (b) are N-vinyllactams, eg. N-vinylpiperidone, N-vinylpyrrolidone and N-vinylcaprolactam, N-vinylacetamide, N-methyl-N-vinylacetamide, acrylamide, methacrylamide, N,N-dimethylacrylamide, N-methylolmethacrylamide, N-vinyloxazolidone, N-vinyltriazole, hydroxyalkyl (meth)acrylates, eg. hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylates, or alkyl ethylene glycol (meth)acrylates having 1 to 50 ethylene glycol units in the molecule.
Suitable monomers (c) are C1-C24-, especially C1-C10-alkyl esters of (meth)acrylic acid, e.g. methyl (meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate and acrylamides such as N-tert-butylacrylamide or N-tert-octylacrylamide. Also suitable are vinyl esters of carboxylic acids, eg. vinyl acetate or vinyl propionate.
Monomers (d), which possess a crosslinking function, are compounds having at least 2 ethylenically unsaturated, nonconjugated double bonds in the molecule.
Suitable crosslinkers are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the parent alcohols may be in fully or partially etherified or esterified form; however, the crosslinkers contain at least two ethylenically unsaturated groups.
Further suitable crosslinkers are the vinyl esters or the esters of monohydric unsaturated alcohols with ethylenically unsaturated C3-C6 carboxylic acids, for example acrylic, methacrylic, itaconic, maleic or fumaric acid.
Other suitable crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, examples being those of oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
The monomers (a) to (d) can in each case be employed individually or in a mixture with other monomers from the same group.
8) Polymers obtained by reacting a polyalkylenepolyamine which comprises two primary amine groups and at least one secondary amine group with a dicarboxylic acid from the group of diglycolic acid and saturated aliphatic dicarboxylic acids having 3 to 8 carbons, the molar ratio of polyalkylenepolyamine to dicarboxylic acid being from 0.8:1 to 1.4:1; the polyamide formed is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine group of the polyamide of from 0.5:1 to 1.8:1,
9) copolymers comprising as main chain constituent units of the formula (III) or (IIIxe2x80x2) 
where 1 and t are 0 or 1 and 1+t=1, Rxe2x80x3 is hydrogen or methyl, R and Rxe2x80x2 independently of one another are alkyl of 1 to 22 carbons, hydroxyalkyl preferably of 1 to 5 carbons, or a lower amidoalkyl group and where R and Rxe2x80x2 together with the nitrogen to which they are attached can be heterocyclic groups, such as piperidyl or morpholinyl, and also the copolymers comprising units of the formula (III) or (IIIxe2x80x2) and units derived preferably from acrylamide or diacetoneacrylamide, and Yxe2x8ax96 is an anion, such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate,
10) quaternary polyammonium compounds of the formula 
where R1 and R2, R3 and R4, which are identical or different, are aliphatic, alicyclic or arylaliphatic radicals of not more than 20 carbons or are lower hydroxyaliphatic radicals, or R1 and R2 and R3 and R4, together or separately, with the nitrogen to which they are attached form heterocyclic rings which if desired include a second heteroatom other than nitrogen, or R1, R2, R3 and R4 are the following group 
where Rxe2x80x23 is hydrogen or lower alkoxyl, Rxe2x80x24 has the following definitions: 
in which Rxe2x80x25 is lower alkyl, Rxe2x80x26 is hydrogen or lower alkyl, Rxe2x80x27 is alkylene and D is a quaternary ammonium group; A and B can be polymethylene groups containing 2 to 20 carbon atoms and being linear or branched, saturated or unsaturated, and incorporated into the main chain there may be one or more aromatic rings such as the following group: 
one or more groups xe2x80x94CH2xe2x80x94Yxe2x80x94CH2xe2x80x94 where Y has the following definitions: O, S, SO, SO2, 
where Xxe2x8ax961 is an amine derived from an organic or inorganic acid, Rxe2x80x28 is hydrogen or lower alkyl, Rxe2x80x29 is lower alkyl, or A and A1 and R3, together with the two atoms to which they are attached, form a piperazine ring; if, moreover, A is linear or branched, saturated or unsaturated alkylene or hydroxyalkylene then B can also denote the following group: xe2x80x94(CH2)nxe2x80x94COxe2x80x94Dxe2x80x94OCxe2x80x94(CH2)n, where D has the following definition:
a) a glycol radical of the formula xe2x80x94Oxe2x80x94Ixe2x80x94Oxe2x80x94 in which Z is a linear or branched hydrocarbon radical or a group corresponding to the following formulae: 
in which x and y are an integer from 1 to 4, which denotes a defined and single degree of polymerization, or are any number from 1 to 4, which denotes an average degree of polymerization;
b) a bis-secondary diamine radical, such as a piperazine derivative,
c) a bis-primary diamine radical of the formula: xe2x80x94NHxe2x80x94Yxe2x80x94NHxe2x80x94, in which Y is a linear or branched hydrocarbon radical or the bivalent radical xe2x80x94CH2xe2x80x94CH2xe2x80x94Sxe2x80x94Sxe2x80x94CH2xe2x80x94CH2xe2x80x94,
d) a urea-derived group of the formula xe2x80x94NHxe2x80x94COxe2x80x94NHxe2x80x94;
n is chosen so that the molecular mass is generally from 1000 to 100,000,
Xxe2x88x92 is an anion,
11) homopolymers or copolymers which are derived from acrylic or methacrylic acid and comprise at least one group of the following formulae: 
in which R1 is hydrogen or CH3; A is linear or branched alkyl of 1 to 6 carbons or a hydroxyalkyl of 1 to 4 carbons; R2, R3 and R4, which are identical or different, are an alkyl of 1 to 18 carbons or a benzyl; R5 and R6 are hydrogen or alkyl of 1 to 6 carbons; Xxe2x88x92 is a methosulfate anion or halide,
12) quaternary copolymers of vinylpyrrolidone-vinylimidazole,
13) polyalkyleneimines,
14) polymeres comprising vinylpyridine or vinylpyridinium groups in the chain,
15) condensates of polyamines and epichlorohydrin,
16) quaternary polyurea compounds (polyureylenes),
17) chitin derivatives,
18) cationic silicone polymers (polymeres silicones).
Polymers selected as the anionic polymer are in particular those from the following group:
polymers comprising carboxyl groups derived from unsaturated mono- or dicarboxylic acids of the following formula: 
in which n is an integer from 0 to 10, A is a methylene group which may be attached to the carbon of the unsaturated group or to an adjacent methylene group, if n is greater than 1, by way of a heteroatom such as oxygen, sulfur, R1, hydrogen, phenyl or benzyl, R2 is hydrogen, lower alkyl or carboxyl, and R3 is hydrogen, lower alkyl, xe2x80x94CH2xe2x80x94COOH, phenyl or benzyl,
polymers which comprise groups derived from sulfonic acids, such as vinylsulfonic, styrenesulfonic, lignosulfonic and naphthalenesulfonic (acid) groups.
Of these, particular preference is given to anionic polymers from the following groups:
A) homo- or copolymers of acrylic or methacrylic acid or salts thereof, copolymers of acrylic acid and acrylamide and salts thereof; sodium salts of polyhydroxycarboxylic acids,
B) copolymers of acrylic or methacrylic acid with a monoethylene monomer which may have been grafted with a polyalkylene glycol and which may be branched; copolymers of the type comprising in their chain an unsubstituted or N-alkylated and/or hydroxyalkylated acrylamide group,
C) copolymers which are derived from crotonic acid and which include in their chain vinyl acetate or vinyl propionate groups with or without other monomers, such as allyl or methallyl esters, vinyl ethers or vinyl esters of a linear or branched saturated carboxylic acid having a long hydrocarbon chain, it being possible for these polymers, if desired, to have been grafted or crosslinked,
D) polymers derived from maleic, fumaric and itaconic acids or their anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and esters thereof; copolymers of maleic acid, citraconic anhydride, itaconic anhydride and an allyl or methallyl ester of an xcex1-olefin, acrylic or methacrylic esters, acrylic or methacrylic acid or vinylpyrrolidone in their chain, it being possible for the anhydride groups to be in monoesterified or monoamidated form,
E) polyacrylamides comprising carboxylate groups.
The hair treatment compositions of the invention are soluble in water, alcohols or water/alcohol mixtures and are therefore easy to apply to the hair. In particular it has been found that despite the anionic or cationic nature of the individual polymers the solubility of the polymer mixture in alcohols is good and that there are no instances of precipitation at the polymer concentrations customary for these compositions. As a result, the compositions are highly suitable for use as VOC 55 or VOC 80 compositions, in other words as mixtures containing alcohols in defined amounts (55 or 80%), respectively.
Particularly suitable alcohols are monoalcohols such as C1-C6-alkanols, especially ethanol or isopropanol, polyalcohols, such as alkylene glycols, especially ethylene glycol, and also glycol ethers and esters having hydroxyl groups.
The pump sprays and pump foams of the invention generally include neutralizing agents such as 2-amino-2-methyl-1-propanol or triethanolamine, for example, in an amount, for example, of from 0.1 to 1% by weight.
Further auxiliaries can also be added to the compositions of the invention, examples being colorants, preservatives, emulsifiers, fragrances, electrolytes, viscosity regulators, foam stabilizers and further customary cosmetic base materials.
The compositions of the invention may also include further polymers in order, for example, to enhance the film-forming properties.
Preferred anionic polymers employed are copolymers of unsaturated mono- or dicarboxylic acids with C1-C4-alkyl esters or with methacrylic or acrylic acid, especially copolymers comprising methacrylic acid and ethyl acrylate units.
Preferred cationic polymers which are employed are copolymers having vinylpyrrolidone units, especially copolymers with vinylcaprolactam and vinylimidazolium methyl sulfate (Polyquaternium 46).
Overall, the polymers are present in the mixtures of the invention in a concentration of from 0.1 to 12% by weight; the cationic polymers in a concentration of from 0.05 to 5 and the anionic polymers in a concentration of from 0.05 to 7% by weight.
The invention additionally provides leave-on hair treatment compositions which are free from propellant gases and from polysiloxane and which comprise in combination, dissolved in a solvent, a copolymer having vinylpyrrolidone units and a copolymer having methacrylic acid and ethyl acrylate units. The statements made above regarding the solvents, stabilizers, auxiliaries and concentrations apply analogously to these hair treatment compositions.
The leave-on hair treatment compositions, i.e. compositions which remain in the hair after use, are preferably in the form of lotions or gels. For these compositions it is particularly important that they achieve strength while avoiding stickiness.
The pH of the hair treatment compositions of the invention is preferably from 5 to 8, in particular from 5 to 7.
The foams produced with the pump foams of the invention are notable for the fact that although they are stable they do not have too firm a consistency; in other words, when applied to the hair they are soft and can be distributed easily. This property is of particular importance in terms of consumer acceptance.